JP6005327B2 - Photosensitive resin composition for dry film photoresist - Google Patents

Description

  The present invention relates to a photosensitive resin composition for dry film photoresist.

  The photosensitive resin composition includes a dry film photoresist (DFR), a liquid photoresist ink (Liquid Photoresist Ink), and the like used for a printed circuit board (PCB) and a lead frame (Lead Frame). Used in the form.

  Currently, not only manufacturing printed circuit boards (PCBs) and lead frames, but also plasma display panel (PDP) rib barriers and other display ITO electrodes, bus address electrodes, black matrix (Black Matrix). The dry film photoresist is also widely used for the production of).

  In general, this type of dry film photoresist is frequently used in applications where it is laminated on copper clad laminates. In relation to this, as an example of a manufacturing process of a printed circuit board (PCB), a pre-treatment process is first performed in order to laminate a copper-clad laminate which is a raw material of a PCB. The pre-treatment process is performed in the order of drilling, deburring, and leveling in the outer layer process, and leveling or pickling is performed in the inner layer process. A bristles brush and a jet pumice process are mainly used in the surface finishing process, and soft etching and 5 wt% sulfuric acid pickling can be performed in the pickling process.

  In order to form a circuit on a copper clad laminate that has undergone a pretreatment process, a dry film photoresist (hereinafter referred to as DFR) is generally laminated on the copper layer of the copper clad laminate. In this step, a DFR photoresist layer is laminated on the copper surface while peeling off the DFR protective film using a laminator. In general, laminating is performed at a speed of 0.5 to 3.5 m / min, a temperature of 100 to 130 ° C., and a heated roll pressure of 10 to 90 psi.

  The printed circuit board that has undergone the laminating process is allowed to stand for 15 minutes or more for stabilization of the board, and then exposed to the DFR photoresist using a photomask on which a desired circuit pattern is formed. When the photomask is irradiated with ultraviolet rays in this process, the photoresist irradiated with the ultraviolet rays starts to be polymerized by the contained photoinitiator at the irradiated portion. First, oxygen in the photoresist is initially consumed, then the activated monomer is polymerized to cause a crosslinking reaction, and then the polymerization reaction proceeds while a large amount of monomer is consumed. On the other hand, the unexposed part exists in a state where the crosslinking reaction has not progressed.

  Next, a developing process for removing unexposed portions of the photoresist is performed. In the case of an alkali developable DFR, 0.8 to 1.2 wt% of an aqueous solution of potassium carbonate and sodium carbonate is used as a developing solution. In this step, the unexposed portion of the photoresist is washed away by a saponification reaction between the binder polymer carboxylic acid and the developer in the developer, and the cured photoresist remains on the copper surface.

  Next, a circuit is formed through different processes according to the inner layer process and the outer layer process. In the inner layer process, a circuit is formed on the substrate through a corrosion (etching) and peeling process, and in the outer layer process, after a plating and tenting process, etching and solder peeling are performed to form a predetermined circuit.

  Generally, the dry film photoresist exposed in the plating process is placed in a strong acid or strong alkaline environment. For these reasons, when the chemical resistance is insufficient, a phenomenon occurs in which the dry film photoresist is detached from the copper clad laminate.

  In particular, when the photosensitive resin composition of the dry film photoresist contaminates the plating solution, the appearance of the substrate subjected to the plating treatment may be discolored or the plating efficiency may be reduced, which may cause disconnection.

  Moreover, the photosensitive resin composition is required to have a release property after curing. If the stripping characteristics are insufficient, it is difficult to strip the resist between the fine wirings in the resist stripping step after the plating process, and the stripping time increases, resulting in a decrease in production efficiency.

  The main object of the present invention is to provide a photosensitive resin composition for dry film photoresists which has a high peeling speed and excellent resistance to a plating solution while maintaining excellent fine line adhesion and resolution.

  In order to achieve the above object, an embodiment of the present invention includes [A] a photopolymerization initiator, [B] an alkali-developable binder polymer, and [C] a photopolymerizable compound. The polymerizable compound includes a compound represented by the following chemical formula 1 ([Chemical Formula 1]), and the weight ratio of [C] photopolymerizable compound to [B] alkali-developable binder polymer is 1: 0.1 to 1. A photosensitive resin composition for dry film photoresists is provided.

上記化学式１において、ｌ＋ｎは２または３の整数であり、ｍは１２〜１８の整数である。

In the above chemical formula 1, l + n is an integer of 2 or 3, and m is an integer of 12-18.

  In a preferred embodiment of the present invention, the photosensitive resin composition comprises 2 to 10% by weight of the photopolymerization initiator [A] and 5 to 40% by weight of the compound represented by the chemical formula 1, based on solid content. % Can be included.

  In a preferred embodiment of the present invention, the photosensitive resin composition comprises 2 to 10 wt% of the photopolymerization initiator [A] and 10 to 35 wt% of the compound represented by the chemical formula 1 based on the solid content. % Can be included.

  The photosensitive resin composition for dry film photoresists according to the present invention has a high peeling speed while maintaining excellent fine line adhesion and resolution, and is excellent in resistance to the plating solution. Can be improved.

  Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is conventional, well known in the art.

  Throughout this specification, when a component “includes” a component, it does not exclude other components, but may include other components, unless specifically stated to the contrary. Means you can.

  The present invention includes [A] a photopolymerization initiator, [B] an alkali-developable binder polymer, and [C] a photopolymerizable compound, wherein the [C] photopolymerizable compound is a compound represented by the following chemical formula 1. And [B] a photosensitive resin composition for dry film photoresists, wherein the weight ratio of the [C] photopolymerizable compound to the alkali-developable binder polymer is 1: 0.1-1. is there.

式中、ｌ＋ｎは２〜３の整数であり、ｍは１２〜１８の整数である。

In the formula, l + n is an integer of 2 to 3, and m is an integer of 12 to 18.

  The photosensitive resin composition for dry film photoresists according to the present invention includes excellent fine film adhesion of dry film photoresists by including at least one compound represented by the above chemical formula 1 in [C] photopolymerizable compound. While maintaining the properties and resolution, the peeling speed is fast, and excellent resistance to the plating solution can be obtained.

  Hereinafter, the present invention will be described in more detail.

[A] Photopolymerization initiator The photopolymerization initiator contained in the photosensitive resin composition for dry film photoresists according to the present invention initiates a chain reaction of photopolymerizable monomers by UV and other radiation. A material that plays an important role in curing dry film photoresist.

  Examples of compounds that can be used as the photopolymerization initiator include anthraquinone derivatives such as 2-methylanthraquinone and 2-ethylanthraquinone; benzoin methyl ether, benzophenone, phenanthrenequinone, 4,4′-bis- (dimethylamino) Mention may be made of benzoin derivatives such as benzophenone.

  In addition, 2,2′-bis (2-chlorophenyl) -4,4′-5,5′-tetraphenylbisimidazole, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenyl Ethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- [4-morpholinophenyl] butane-1 -One, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxymethoxy) phenyl] -2-hydroxy- 2-methylpropan-1-one, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- Dodecylphenyl) -2hydroxy-2-methylpropan-1-one, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4 -Dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone β-methoxy diethyl acetal, 1-fluoro Phenyl-1,2-propyldioxime-o, o ′-(2-carbonyl) ethoxy ether, methyl o-benzoylbenzoate, bis [4-dimethylaminophenyl) ketone, 4,4′-bis (diethylamino) benzophenone, 4,4′-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α-dichloro-4-phenoxyacetophenone A compound selected from among pentyl 4-dimethylaminobenzoate can be used as a photopolymerization initiator, but is not limited thereto.

  The photopolymerization initiator is contained in an amount of 2 to 10% by weight based on the solid content, based on the total weight of the photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained.

[B] Alkali developable binder polymer The alkali developable binder polymer of the present invention is a copolymer of (meth) acrylic acid and (meth) acrylic acid ester. Specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy A copolymerized acrylic acid polymer obtained by copolymerization of two or more monomers selected from linear acrylic acid polymers synthesized from propyl methacrylate, acrylamide, methacrylamide, styrene, and α-methylstyrene.

  The alkali-developable binder polymer of the present invention has a weight average molecular weight of 30,000 to 150,000 and a glass transition temperature in consideration of the coating properties of dry film photoresist, followability, and mechanical strength of the resist itself after circuit formation. It is a high molecular compound of 20 to 150 ° C., and it is preferably contained in the photosensitive resin composition at a content in which the weight ratio of the photopolymerizable compound to the alkali-developable binder polymer is 1: 0.1 to 1. When the alkali-developable binder polymer satisfies the weight ratio of the photopolymerizable compound, it is possible to obtain an effect of enhancing the fine wire adhesion after circuit formation.

In the above or below, the weight average molecular weight is measured using Waters 450 GPC with polystyrene as the standard, the columns are Shodex 10 ⁵ , 10 ⁴ , 10 ³ , and the glass transition temperature is DSC7 manufactured by Perkin Elmer. And measured.

[C] Photopolymerizable compound As the photopolymerizable compound of the present invention, a compound represented by the following chemical formula 1 is used alone, or it is used together with a monomer containing at least two ethylene groups at its terminals. Can do.

式中、ｌ＋ｎは２または３の整数であり、ｍは１２〜１８の整数である。

In the formula, l + n is an integer of 2 or 3, and m is an integer of 12-18.

  The compound represented by the chemical formula 1 can improve the hydrophobicity of the photosensitive resin composition, remarkably increase the resistance to the developing solution and the plating solution, and shorten the peel time of the cured film. The fact that the photosensitive resin composition is excellent in resistance to the plating solution means that the plating solution is not contaminated and therefore has little influence on the appearance and color of the plating.

  In this invention, it is preferable to contain the compound represented by the said Chemical formula 1 with 5 to 40 weight% with respect to the total weight of solid content of the photosensitive resin composition, More preferably, it contains with 10 to 35 weight%.

  If the content of the compound represented by the chemical formula 1 is less than 5% by weight with respect to the total weight of the solid content of the photosensitive resin composition, the effect accompanying the addition of the compound represented by the chemical formula 1 Is insufficient, and when it exceeds 40% by weight, there is a possibility that a problem that the peeling time rapidly increases may occur.

  The photopolymerizable compound of the present invention may contain a monomer containing at least two ethylene groups at its terminals in addition to the compound represented by the above chemical formula 1.

  Examples of the monomer containing at least two ethylene groups at the terminal include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate glycol, and ethylene glycol dimethacrylate. (Propylene glycol dimethacrylate), polypropylene glycol dimethacrylate (polypropylene glycol dimethacrylate), butylene glycol dimethacrylate (butylene glycol dimethacrylate) thacrylate), neopentyl glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylpropylenetriacrylate ), Glycerin dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate. (Pentaerythritol trimethacrylate), dipentaerythritol pentamethacrylate (dipentaerythritol pentamethacrylate), 2,2-bis (4-methacryloxydiethoxyphenyl) propane (2,2-bis (4-methacryloxydiethylphenylpropylene), Bis (4-methacryloxypolyethoxyphenyl) propane (2,2-bis (4-methacryloxyphenyl) propane), 2-hydroxy-3-methacryloyloxypropyl methacrylate (2-hydroxy-3-methyoxypropyl methacrylate), Ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, phthalate diglyceryl diglyceryl diglyceryl ester (Glycerin polyglycidyl ether polymethacrylate), polyfunctional (meth) acrylate containing a urethane group, etc. can be mentioned.

  Moreover, it is preferable that the weight ratio of the [C] photopolymerizable compound with respect to the said [B] alkali developable binder polymer is 1: 0.1-1. When the weight ratio of the photopolymerizable compound is within the above range, an effect of enhancing photosensitivity, resolution, adhesion, and the like can be obtained.

[D] Solvent and other additives The solvent of the photosensitive resin composition of the present invention is generally limited to those selected from methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone. The content can also be adjusted according to the content of the photopolymerization initiator, the alkali-developable binder polymer and the photopolymerizable compound.

  Moreover, the photosensitive resin composition of the present invention may further contain other additives as necessary, but the “other additives” are plasticizers, and are (1) phthalate esters. Dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate in the form; (2) triethylene glycol diacetate, tetraethylene glycol diacetate in the form of glycol ester; (3) p-toluene sulfone in the form of acid amide Amide, benzenesulfonamide, n-butylbenzenesulfonamide; (4) triphenyl phosphate, and the like can be used.

  In the present invention, in order to improve the handleability of the photosensitive resin composition, a leuco dye or a coloring substance can be added. Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, and fluorane dye. Among them, when leuco crystal violet is used, the contrast is favorable and preferable. When the leuco dye is contained, the content is preferably 0.1 to 10% by weight with respect to the photosensitive resin composition. From the viewpoint of developing contrast, it is preferably 0.1% by weight or more, and from the viewpoint of maintaining storage stability, it is preferably 10% by weight or less.

  Examples of coloring substances include toluenesulfonic acid monohydrate, fuchsin, phthalocyanine green, auramin base, paramagenta, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green, diamond green, basic blue 20 and the like. Can be mentioned. When the coloring material is contained, the addition amount is preferably 0.001 to 1% by weight with respect to the photosensitive resin composition. A content of 0.001% by weight or more has an effect of improving handleability, and a content of 1% by weight or less has an effect of maintaining storage stability.

  Other additives may further include a thermal polymerization inhibitor, a dye, a discoloring agent, an adhesion promoter, and the like.

  In the present invention, the photosensitive resin composition having the above-described composition can be produced as a photosensitive resin composition for dry film photoresist, and is coated on a normal substrate film such as polyethylene terephthalate. The photosensitive resin layer is coated to a thickness of 5 to 200 μm using a method, and then dried, and an ordinary protective film such as polyethylene is laminated on the upper surface of the dried photosensitive resin layer to produce a dry film. be able to. The dry film thus produced is exposed and developed to evaluate each physical property.

Hereinafter, preferred examples and comparative examples of the present invention will be described. However, the following embodiment is only a preferred embodiment of the present invention and does not limit the present invention.
[Production Example 1]
A four-necked round bottom flask was equipped with a mechanical stirrer and a reflux apparatus, and then the inside of the flask was purged with nitrogen. The nitrogen purged flask was charged with 90 g of MEK (Methyl Ethyl Ketone) and 10 g of PGMEA (Propylene Glycol Monoethyl Ether Acetate), and then charged with azobisisobutyronitrile (Azobisisobutyronitrile), 0.8 g Dissolved. A monomer mixture of 20 g of methyl methacrylic acid, 70 g of methyl methacrylate and 10 g of styrene monomer was added thereto, and the temperature was raised to 80 ° C., followed by polymerization for 6 hours to produce an alkali developable binder polymer.
[Production Examples 2 to 4]
The compound represented by Chemical Formula 1 of the present invention was produced by the following method.

1) Synthesis of PEO-PPO-PEO block copolymer Poly (propylene glycol) [40 mmol] and KOH [6 g] as a basic catalyst were placed in an autoclave and heated at 120 ° C. in an N ₂ atmosphere, followed by ethylene oxide. The solution (132 mL for Production Examples 2 to 3 and 88 mL for Production Example 4) was added dropwise dropwise to synthesize a PEO-PPO-PEO block copolymer. After completion of the reaction, the solvent and water were removed by filtration under reduced pressure.

  Table 1 below shows the poly (propylene glycol) used in Production Examples 2-4.

2) Synthesis of Pluronic Diacrylate A round bottom flask equipped with a funnel and a nitrogen inlet was placed in an ice bath, and the previously synthesized PEO-PPO-PEO block was added to the round bottom flask. A polymer (30 mmol), triethylamine (71.4 mmol, 7.22 g) and methylene chloride (150 mL) were added. Then, methacryloyl chloride (73.78 mmol, 7.71 g) was added dropwise over 3 hours and left to react for another 20 hours. Meanwhile, the inside of the flask was continuously purged with nitrogen while maintaining the temperature between 0 ° C and 25 ° C. Filtered under reduced pressure to remove the salt form byproduct and lyophilized to remove water.

  Table 2 below shows the compounds represented by Chemical Formula 1 produced by Production Examples 2 to 4.

3) The molecular weights of the compounds produced in Production Examples 2 to 4 were measured by GPC as follows.
<Method for measuring molecular weight by GPC>
The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC) (Waters Alliance e2695 + Waters 2414 RI Detector). The polymer to be measured was dissolved in tetrahydrofuran to a concentration of 0.2%, then filtered through a 0.45 μm PTFE syringe filter, and 10 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC and was introduced at a flow rate of 1.0 mL / min, and analysis was performed at 30 ° C. For the column, two Plgel Mixed Ds manufactured by Agilent were connected in series. Measurement was performed at 40 ° C. using an RI detector as a detector. A calibration curve was prepared by injecting polystyrene standard dissolved in THF at a concentration of 0.1%.

[Examples 1 to 13 and Comparative Examples 1 to 3]
The photosensitive resin composition for dry film photoresist was blended and coated according to the compositions shown in Tables 3 and 4 below and evaluated. First, after dissolving photoinitiators in methyl ethyl ketone (MEK) as a solvent, the photopolymerizable compound and the alkali-developable binder polymer of Production Example 1 are added and mixed for about 1 hour using a mechanical stirrer. Thus, a photosensitive resin composition was obtained. The obtained photosensitive resin composition was coated on a 40 μm PET film using a coating bar. The coated photosensitive resin composition layer is dried using a hot air oven. At this time, the drying temperature is 80 ° C., the drying time is 5 minutes, and the thickness of the photosensitive resin composition layer after drying is as follows. Was 40 μm. The dried film was laminated using a protective film (polyethylene) on the photosensitive resin layer.

（注）
（１）ＥＡＢ：４，４−（ビスジエチルアミノ）ベンゾフェノン（Ａｌｄｒｉｃｈ Ｃ
ｈｅｍｉｃａｌ）
（２）ＢＣＩＭ：２，２−ビス−（２−クロロフェニル−４，５，４，５−テトラフェ
ニルビスイミダゾール（Ａｌｄｒｉｃｈ Ｃｈｅｍｉｃａｌ）
＊ メチルメタクリル酸／メチルメタクリレート／スチレンモノマー共重合体（２０：
７０：１０の重量比）、重量平均分子量６０，０００
（３）製造例２：本発明の化学式１において、ｌ＋ｎは３であり、ｍは１８である。
（４）Ｍ−２０５３：本発明の化学式１において、ｌ＋ｎは６であり、ｍは１２である
（ミウォンスペシャルティケミカル）。
（５）ＢＰＥ−５００：２，２−ビス［４−（メタクリルオキシポリエトキシ）フェニ
ル］プロパン（２，２−ｂｉｓ［４−（ｍｅｔｈａｃｒｙｌｏｘｙｐｏｌｙｅｔｈｏｘ
ｙ）ｐｈｅｎｙｌ］ｐｒｏｐａｎｅ）（新中村）
（６）ロイコクリスタルバイオレット：日本Ｈｏｄｏｇａｙａ Ｃｏ．
（７）ダイヤモンドグリーンＧＨ：日本Ｈｏｄｏｇａｙａ Ｃｏ．

(note)
(1) EAB: 4,4- (bisdiethylamino) benzophenone (Aldrich C)
chemical)
(2) BCIM: 2,2-bis- (2-chlorophenyl-4,5,4,5-tetraphenylbisimidazole (Aldrich Chemical)
* Methyl methacrylic acid / methyl methacrylate / styrene monomer copolymer (20:
70:10 weight ratio), weight average molecular weight 60,000
(3) Production Example 2: In Chemical Formula 1 of the present invention, l + n is 3 and m is 18.
(4) M-2053: In the chemical formula 1 of the present invention, l + n is 6 and m is 12 (Miwon Specialty Chemical).
(5) BPE-500: 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (2,2-bis [4- (methacryloxypolyethox)
y) phenyl] propane) (Shin Nakamura)
(6) Leuco Crystal Violet: Nippon Hodogaya Co.
(7) Diamond Green GH: Nippon Hodoya Co.

  Table 4 below shows the contents of the photopolymerizable compounds in Examples 6 to 13, respectively. The rest of the composition excluding the photopolymerizable compound is the same as in Example 1.

前記組成によって製造された感光性樹脂組成物を用いて製造されたドライフィルムフォトレジストについて、次の工程を行った。

The following process was performed on the dry film photoresist produced using the photosensitive resin composition produced according to the above composition.

<Laminate>
The dry film photoresist is applied to a 1.6 mm thick copper-clad laminate subjected to brush polishing treatment, a substrate preheating roll temperature of 120 ° C., a lamination roll temperature of 115 ° C., a roll pressure of 4.0 kgf / cm ² , and a roll speed. Lamination was performed using HAKUTO MACH 610i under the condition of 2.5 min / m.

<Development and resolution>
The dry film photoresist laminated on the copper-clad laminate was irradiated with ultraviolet light at an exposure amount of 40 mJ using a Perkin-Elmer ™ OB7120 (parallel light exposure machine) using a photomask for circuit evaluation, and left for 20 minutes. Thereafter, development was performed on a Na ₂ CO ₃ 1.0 wt% aqueous solution under the spray jet development conditions. The time taken for the dry film photoresist on the copper-clad laminate to be completely washed away with the developer was measured using a stopwatch (minimum development time). Fixed (twice the minimum development time).

  The physical properties of dry film photoresists produced using the photosensitive resin compositions produced in Examples 1 to 13 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 5 below.

<Fine wire adhesion (unit: μm)>
This is the minimum line width at which an independent resist remains after development. Measured with a ZEISS AXIOPHOT Microscope.

<Resolution (unit: μm)>
It was a value measured by setting the space between the circuit lines to 1: 1, and was measured with a ZEISS AXIOPHOT Microscope.

<Evaluation of contamination against plating>
The dry film photoresist manufactured from the photosensitive resin composition is cut into a size of 40 cm × 50 cm, the protective film is removed, and the step tablet is exposed with an exposure amount of 20 steps, and then the PET film is peeled off. Thus, a cured film was obtained. This cured film was immersed in 1 L of a plating solution of an aqueous solution of copper sulfate / sulfuric acid for 3 days. The copper plate was subjected to electrolytic copper plating at a current of 2 A for 15 minutes using a Hull cell test bath (manufactured by Jonde Test Laboratory, Korea).

  If the plating solution that does not immerse the cured film is used as a reference, and the plating appearance when plating with the plating solution that immerses the cured film is observed with the naked eye, if the plating appearance is abnormal or discoloration occurs X: Same as reference, and when there was no abnormality, it was judged as “good”.

<Peeling speed (unit: seconds)>
After removing the PE film of the produced photosensitive dry film resist, it is laminated on a copper plate using a thermocompression-bonding roller, and the photosensitive resin composition is exposed and developed to form a photocured film having a size of 50 mm × 50 mm. Manufactured. Then, peeling was performed using a 3% aqueous sodium hydroxide solution (temperature: 50 ° C.). The peeling speed was evaluated by measuring the time for the photocured film to peel from the copper plate.

^※１細線密着力は、現像の後、独立した線幅が生き残っている最小線幅である。
^※２解像度は、回路ラインと回路ラインとの間の空間を１：１にして測定した値である。

^{* 1} Fine line adhesion is the minimum line width at which an independent line width survives after development.
^{* 2} Resolution is a value measured with a space between circuit lines of 1: 1.

  As shown in Table 5 above, Examples 1 to 13 have a high peeling speed while maintaining a similar level of fine wire adhesion and resolution as compared with Comparative Examples 1 to 3, and are extremely excellent in resistance to plating solutions. I was able to know. In particular, in the case of Comparative Example 3, since the photosensitive resin composition layer was too viscous and the film shape could not be properly maintained, the lamination step could not be performed.

Any simple variations or modifications of the present invention can be easily implemented by those having ordinary knowledge in the art, and it can be understood that all such variations and modifications are included in the scope of the present invention.

Claims (3)

[A] a photopolymerization initiator, [B] an alkali-developable binder polymer, and [C] a photopolymerizable compound, wherein the [C] photopolymerizable compound is represented by the following chemical formula 1 ([Chemical Formula 1]) A photosensitive resin composition for dry film photoresists comprising a compound, wherein the weight ratio of [C] photopolymerizable compound to [B] alkali-developable binder polymer is 1: 0.1-1.

In the above chemical formula 1, l + n is an integer of 2 or 3, and m is an integer of 12-18.   The photosensitive resin composition includes 2 to 10% by weight of the photopolymerization initiator [A] and 5 to 40% by weight of the compound represented by the chemical formula 1, based on solid content. Item 2. A photosensitive resin composition for dry film photoresists according to Item 1.   The photosensitive resin composition contains 2 to 10% by weight of a photopolymerization initiator [A] and 10 to 35% by weight of a compound represented by Chemical Formula 1, based on solid content. The photosensitive resin composition for dry film photoresists described in 1.